CN105417981A - Alkali-free liquid accelerating agent and preparing method thereof - Google Patents
Alkali-free liquid accelerating agent and preparing method thereof Download PDFInfo
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- CN105417981A CN105417981A CN201510912656.5A CN201510912656A CN105417981A CN 105417981 A CN105417981 A CN 105417981A CN 201510912656 A CN201510912656 A CN 201510912656A CN 105417981 A CN105417981 A CN 105417981A
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- free liquid
- alkali
- liquid accelerator
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/10—Accelerators; Activators
- C04B2103/12—Set accelerators
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Aftertreatments Of Artificial And Natural Stones (AREA)
Abstract
The invention discloses an alkali-free liquid accelerating agent. The alkali-free liquid accelerating agent is a high-strength alkali-free liquid accelerating agent prepared from, by mass, 5%-6% of triethanolamine, 16%-18% of aluminum sulfate, 26%-30% of magnesium fluoride and the balance water and used for concrete with the strength grade higher than C50, or is a low-strength alkali-free liquid accelerating agent prepared from, by mass, 42%-45% of aluminum sulfate, 5%-8% of magnesium fluoride and the balance water and used for concrete with the strength grade lower than C50. As the alkali-free liquid accelerating agent is produced through the magnesium fluoride prepared through fluorine-containing waste gas, the accelerating effect of the alkali-free liquid accelerating agent is remarkably improved, and the compressive strength, the anti-permeability and the frost resistance of the concrete are remarkably improved.
Description
Technical field
The present invention relates to accelerating chemicals technical field, be specifically related to a kind of alkali-free liquid accelerator and preparation method thereof.
Technical background
Accelerating chemicals mixes the admixture that can make the rapid setting and harden of concrete in concrete, is indispensable additive in construction of shotcrete method, accelerates the hydration and hardening of cement, form enough intensity in a short period of time, to ensure the requirement of special construction.Along with the development of technology, current alkali-free liquid accelerator is development trend, and be generally aluminium salt and the solution that is composited of acid or suspension, its alkali content is generally and is less than 1%, is mainly used in the sprayed concrete of tunnel, mine or the project of reinforcing.Due to not chloride ion-containing, basic ion in alkali-free liquid accelerator, thus can not Corrosion Reinforcement, free from environmental pollution, the health that do not injure operating personnel.
As CN200810203051.9 discloses a kind of environment-friendly type alkali-free liquid accelerator for sprayed concrete and preparation method thereof, it is made up of Tai-Ace S 150, Sodium Fluoride, trolamine and polyacrylamide.The early stage behavior of hydrated cementitious mainly affects by C3A reaction, and the development of condensation and early strength depends primarily on the extent of hydration of silicate especially C3S.The application of a large amount of Tai-Ace S 150 has certain promoter action to hydrated cementitious, but introduce the content overproof that sulphur trioxide makes sulphur trioxide in cement simultaneously, when Sulfates accelerating chemicals volume is higher, the existence of sulfate ion produces detrimentally affect to concrete endurance quality.
CN10891852A discloses a kind of alkali-free liquid accelerator, wherein, it comprises according to mass percent: Patent alum: 48%-58%, Calcium Fluoride (Fluorspan): 3%-5%, organic alcohol amine: 1.5%-3.5%, Mierocrystalline cellulose: 0.2%-0.5%, high molecular polymer: 0.2%-0.5%, earthy mineral: 3%-6%, surplus is water.Its complexity of filling a prescription, preparation cost is high, is unfavorable for that industrialized development technique is more complicated, and
It is the alkali-free liquid accelerator of main rapid hardening composition that patent CN201110112424 discloses with Tai-Ace S 150, and organic amine, as the glutinous component of increasing, improves jetted layers thickness, reduce rebound loss, but such accelerating chemicals can cause the loss of later strength.
Patent US2002035952A1 discloses a kind of preparation method of alkali-free liquid accelerator, use hydrofluoric acid dissolution Tai-Ace S 150 and the aluminium hydroxide of 40% concentration, and add organic amine 4.5 ~ 7.5%, wherein the content of Tai-Ace S 150 is 20 ~ 40%, and aluminium hydroxide content is 10%.Although Al
3+to the acceleration condensation of hydrated cementitious, there is good promoter action, but the solvability extreme difference of aluminium-hydroxide powder, present nonionic form in aqueous, have obvious demixing phenomenon with other mixtures are miscible, directly affects its short solidifying effect.
In addition, production of phosphate fertilizer enterprise produces a large amount of main components when producing phosphoric acid, diammonium phosphate, general calcium, coarse whiting, secondary calcium phosphate is HF and SiF
4waste gas containing fluoride, directly discharge can atmosphere pollution.
Summary of the invention
The object of this invention is to provide a kind of novel alkali-free liquid accelerator and preparation method thereof.
Technical scheme of the present invention is as follows:
A kind of alkali-free liquid accelerator, it is made up for the high strength alkali-free liquid accelerator in the above concrete of strength grade C50 of trolamine, Tai-Ace S 150, magnesium fluoride and water, or make for the low strength alkali-free liquid accelerator in the following concrete of strength grade C50 by Tai-Ace S 150, magnesium fluoride and water;
In described high strength alkali-free liquid accelerator, the mass percent of each component is: trolamine 5 ~ 6%, Tai-Ace S 150 16 ~ 18%, magnesium fluoride 26 ~ 30%, water polishing to 100%;
In described low strength alkali-free liquid accelerator, the mass percent of each component is: Tai-Ace S 150 42 ~ 45%, magnesium fluoride 5 ~ 8%, water polishing to 100%.
Further scheme, described magnesium fluoride is decomposed after neutralization reaction by silicofluoric acid and magnesium oxide to obtain.
Further scheme, the usage quantity of described high strength alkali-free liquid accelerator is 5.0% ~ 8.0% of gelling material weight in concrete; The usage quantity of described low strength alkali-free liquid accelerator is 6.0% ~ 8.0% of gelling material weight in concrete.
Another goal of the invention of the present invention is to provide the preparation method of above-mentioned a kind of alkali-free liquid accelerator, and its step is as follows:
(1) the waste gas containing fluoride water that production phosphate fertilizer produces absorbed and filters, obtaining silicate fluoride solution;
(2) magnesium oxide is added in silicate fluoride solution carry out neutralization reaction, to filter after elimination throw out to obtain magnesium silicofluoride solution;
(3) to magnesium silicofluoride solution warms to evaporating at 105-500 DEG C, concentrated 1-6h, be decomposed into magnesium fluoride;
(4) magnesium fluoride is carried out after cooling and Tai-Ace S 150, water stirring and dissolving obtain low strength alkali-free liquid accelerator, or magnesium fluoride and trolamine, Tai-Ace S 150, water stirring and dissolving are obtained high strength alkali-free liquid accelerator.
Further scheme, in described step (2), the mass ratio of magnesium silicofluoride and magnesium fluoride is 1:0.28.
Further scheme, in described step (3), evaporation, decomposition produces SiF simultaneously
4gas and water of condensation, by SiF
4gas carries out the reaction raw materials that recovery is used as step (1), and water of condensation is returned boiler.
The present invention utilizes production of phosphate fertilizer enterprise to produce a large amount of main components for HF and SiF when producing phosphoric acid, diammonium phosphate, general calcium, coarse whiting, secondary calcium phosphate
4waste gas containing fluoride, as raw material, absorb obtained silicate fluoride solution with water to it, its chemical equation is as follows:
3SiF
4+3H
2O=2H
2SiF
6+SiO
2·H
2O
2HF+SiF
4=H
2SiF
6
Then become magnesium silicofluoride with obtained silicofluoric acid with magnesium fluoride building-up reactions, then intensification is decomposed into magnesium fluoride and SiF
4, wherein magnesium fluoride prepares alkali-free liquid accelerator as raw material, SiF
4recovery is done raw material and is used.Its chemical equation is as follows:
H
2SiF
6+MgO=MgSiF
6+H
2O
MgSiF
6=MgF
2+SiF
4
In the present invention, in concrete, gelling material mainly refers to cement, flyash and breeze.
The present invention has following beneficial effect:
1, the present invention selects not containing alkali-free liquid accelerator prepared by inorganic salt and the organic materials of potassium sodium, wherein alkali content < 0.1%.Thus corrodibility injury can not be produced to people, reinforcing bar and instrument etc. when constructing, and reduce destruction concrete caused owing to introducing alkaline matter dramatically, can dust concentration and springback capacity etc. be reduced in course of injection.
2, the accelerating mechanism of alkali-free liquid accelerator prepared of the present invention is for eliminating C
3the inductive phase of S, at the aquation initial stage, generate hydrated calcium silicate crystal and the Aft crystal of pin column, the rapid nucleation of these crystal, to grow up, mutual intersection adhesion forms network structure, makes the rapid initial set of cement slurry, and hydrated product thereafter continues filling concrete void among particles, make the rapid final set of cement slurry, thus substantially increase its rapid hardening effect.
3, the alkali-free liquid accelerator that prepared by the present invention can significantly improve concrete ultimate compression strength, impermeability and anti-freezing property.
4, the present invention utilize phosphate fertilizer plant to produce fluorine waste gas as starting material to produce magnesium fluoride; both solved the environmental issue in phophatic fertilizer production process, again this fluorine waste gas had been reused, and do not produced second time and pollute; and whole technological process, without waste gas, discharging of waste liquid, guarantees environment protection standard.
5, the present invention adopts magnesium fluoride as the critical material of alkali-free liquid accelerator, plays great promoter action to cement multiviscosisty, and can provide comparatively ideal short solidifying effect, has opened up the Application Areas of magnesium fluoride.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1:
(1) the waste gas containing fluoride water that production phosphate fertilizer produces absorbed and filters, obtaining silicate fluoride solution;
(2) magnesium oxide is added in silicate fluoride solution carry out neutralization reaction, to filter after elimination throw out to obtain magnesium silicofluoride solution; Wherein the mass ratio of magnesium silicofluoride and magnesium fluoride is 1:0.28;
(3) evaporate at magnesium silicofluoride solution warms to 105 DEG C, concentrated 1h, be decomposed into magnesium fluoride; Evaporation, decomposition produces SiF simultaneously
4gas and water of condensation, by SiF
4gas carries out the reaction raw materials that recovery is used as step (1), and water of condensation is returned boiler;
(4) take cooled magnesium fluoride 3000kg and Tai-Ace S 150 1600g, trolamine 500g, water 4900g together mixes to and dissolve completely, obtained high strength alkali-free liquid accelerator.
Embodiment 2:
(1) the waste gas containing fluoride water that production phosphate fertilizer produces absorbed and filters, obtaining silicate fluoride solution;
(2) magnesium oxide is added in silicate fluoride solution carry out neutralization reaction, to filter after elimination throw out to obtain magnesium silicofluoride solution; Wherein magnesium silicofluoride 5 is 1:0.28 with the mass ratio of magnesium fluoride;
(3) evaporate at magnesium silicofluoride solution warms to 500 DEG C, concentrated 6h, be decomposed into magnesium fluoride; Evaporation, decomposition produces SiF simultaneously
4gas and water of condensation, by SiF
4gas carries out the reaction raw materials that recovery is used as step (1), and water of condensation is returned boiler;
(4) take cooled magnesium fluoride 2600g and Tai-Ace S 150 1800g, trolamine 600g, water 5000g together mixes to and dissolve completely, obtained high strength alkali-free liquid accelerator.
Embodiment 3:
(1) the waste gas containing fluoride water that production phosphate fertilizer produces absorbed and filters, obtaining silicate fluoride solution;
(2) magnesium oxide is added in silicate fluoride solution carry out neutralization reaction, to filter after elimination throw out to obtain magnesium silicofluoride solution; Wherein the mass ratio of magnesium silicofluoride and magnesium fluoride is 1:0.28;
(3) evaporate at magnesium silicofluoride solution warms to 300 DEG C, concentrated 2h, be decomposed into magnesium fluoride; Evaporation, decomposition produces SiF simultaneously
4gas and water of condensation, by SiF
4gas carries out the reaction raw materials that recovery is used as step (1), and water of condensation is returned boiler;
(4) take cooled magnesium fluoride 500kg and Tai-Ace S 150 4500g, water 5000g together mixes to and dissolve completely, obtained low strength alkali-free liquid accelerator.
Embodiment 4:
(1) the waste gas containing fluoride water that production phosphate fertilizer produces absorbed and filters, obtaining silicate fluoride solution;
(2) magnesium oxide is added in silicate fluoride solution carry out neutralization reaction, to filter after elimination throw out to obtain magnesium silicofluoride solution; Wherein magnesium silicofluoride 5 is 1:0.28 with the mass ratio of magnesium fluoride;
(3) evaporate at magnesium silicofluoride solution warms to 400 DEG C, concentrated 4h, be decomposed into magnesium fluoride; Evaporation, decomposition produces SiF simultaneously
4gas and water of condensation, by SiF
4gas carries out the reaction raw materials that recovery is used as step (1), and water of condensation is returned boiler;
(4) take cooled magnesium fluoride 800g and Tai-Ace S 150 4200g, water 5000g together mixes to and dissolve completely, obtained low strength alkali-free liquid accelerator.
Comparative example 1:
Adopt embodiment 1 in patent CN104891852A as a comparison case 1, it is made up of the component of following masses per-cent: Patent alum: 52%, Calcium Fluoride (Fluorspan) CaF2:4.5%, organic alcohol amine: 3%, Mierocrystalline cellulose: 0.2%, high molecular polymer: 0.4%, earthy mineral: 5%, surplus is water.During preparation, according to the common process of this area, each component is mixed.
Embodiment 5: alcohol coagulation test
Alkali-free liquid accelerator prepared by the embodiment of the present invention 1,2 and comparative example 1 is detected its initial set, final setting time, shown in table 1 specific as follows respectively:
Table 1: time of coagulation
| Time of coagulation | Examination criteria | Embodiment 1 | Embodiment 2 | Comparative example 1 |
| Initial set/min | JC477-2005 | 2:52 | 2:40 | 3:20 |
| Final set/mm | JC477-2005 | 5:30 | 5:10 | 6:10 |
Can find out from upper table 1, the initial set of alkali-free liquid accelerator prepared by the present invention, final setting time are all significantly shorter than time of coagulation in comparative example 1, illustrate that the rapid hardening of alkali-free liquid accelerator prepared by the present invention is effective.
Embodiment 6: compressive strength test
The embodiment of the present invention 1,2 is mixed with high-strength shotcrete with alkali-free liquid accelerator prepared by comparative example 1 according to identical component and consumption, and form concrete 1, concrete 2, concrete 3, its three kinds of concrete composition and ratios are all as shown in table 2 below:
Table 2: concrete composition
| Strength grade | Cement type | Water | Stone | Sand | Cement | Accelerating chemicals | Water reducer |
| C50 | Reference cement | 165 | 925 | 788 | 516 | 25.8 | 7.7 |
Three kinds of concrete are used and are detected its ultimate compression strength respectively by JC477-2005 examination criteria, shown in table 3 specific as follows in latter 28 days:
Table 3: ultimate compression strength
| Intensity | Examination criteria | Concrete 1 | Concrete 2 | Concrete 3 |
| 28 days ultimate compression strength | JC477-2005 | 65.7MPa | 60MPa | 55.4MPa |
Can find out from upper table 3, the ultimate compression strength of concrete 1,2 significantly improves the ultimate compression strength of concrete 3, illustrates that alkali-free liquid accelerator prepared by the present invention can significantly improve concrete ultimate compression strength.
Embodiment 7: Standard Test Method for Permeation Resistance
The embodiment of the present invention 1,2 is mixed with high-strength shotcrete with alkali-free liquid accelerator prepared by comparative example 1 according to identical component and consumption, forms concrete 4, concrete 5, concrete 6, shown in its three kinds of concrete formulation tables 4 composed as follows:
Table 4: concrete composition
| Cement type | Water | Stone | Sand | Cement | Accelerating chemicals | Water reducer |
| Reference cement | 188 | 899 | 899 | 418 | 25.1 | 5.85 |
To concrete 4, concrete 5, concrete 6 and the high-strength shotcrete 7 not adding accelerating chemicals, carry out impermeability and frost resistance experiment respectively.Because the seepage-resistant grade of sprayed concrete is very high, therefore, when carrying out Standard Test Method for Permeation Resistance to it, when should take pressure as 3.0MPa, the permeated height of moisture in concrete be to evaluate its anti-permeability performance.Shown in table 5 specific as follows:
Table 5: impervious and anti-freezing property
| Impervious | Examination criteria | Concrete 4 | Concrete 5 | Concrete 6 | Concrete seven |
| Permeated height/mm | GB/T50082-2009 | 110 | 105 | 150 | 140 |
| 200 circulation Relative dynamic modulus of elasticity/% | GB/T50082-2009 | 83.0 | 75.6 | 64.3 | 62.8 |
| 250 circulation Relative dynamic modulus of elasticity/% | GB/T50082-2009 | 64.3 | 58.3 | 45 | 37.0 |
Can find out from upper table 5, the permeated height of concrete 4,5 is significantly less than the permeated height of concrete 6,7, thus illustrates that alkali-free liquid accelerator prepared by the present invention can significantly improve concrete impermeability.In addition, 200 circulation Relative dynamic modulus of elasticities of concrete 4,5 are more than 75%, 250 times circulation Relative dynamic modulus of elasticity is more than 58%, is all significantly higher than the circulation Relative dynamic modulus of elasticity of concrete 6,7, so illustrate that alkali-free liquid accelerator prepared by the present invention can significantly improve concrete anti-freezing property.
Above-mentioned is can understand and apply the invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.
Claims (6)
1. an alkali-free liquid accelerator, it is characterized in that: it is made up for the high strength alkali-free liquid accelerator in the above concrete of strength grade C50 of trolamine, Tai-Ace S 150, magnesium fluoride and water, or make for the low strength alkali-free liquid accelerator in the following concrete of strength grade C50 by Tai-Ace S 150, magnesium fluoride and water;
In described high strength alkali-free liquid accelerator, the mass percent of each component is: trolamine 5 ~ 6%, Tai-Ace S 150 16 ~ 18%, magnesium fluoride 26 ~ 30%, water polishing to 100%;
In described low strength alkali-free liquid accelerator, the mass percent of each component is: Tai-Ace S 150 42 ~ 45%, magnesium fluoride 5 ~ 8%, water polishing to 100%.
2. a kind of alkali-free liquid accelerator according to claim 1, is characterized in that: described magnesium fluoride is decomposed after neutralization reaction by silicofluoric acid and magnesium oxide to obtain.
3. a kind of alkali-free liquid accelerator according to claim 1, is characterized in that: the usage quantity of described high strength alkali-free liquid accelerator is 5.0% ~ 8.0% of gelling material weight in concrete; The usage quantity of described low strength alkali-free liquid accelerator is 6.0% ~ 8.0% of gelling material weight in concrete.
4. a preparation method for a kind of alkali-free liquid accelerator as claimed in claim 1, is characterized in that: step is as follows:
(1) the waste gas containing fluoride water that production phosphate fertilizer produces absorbed and filters, obtaining silicate fluoride solution;
(2) magnesium oxide is added in silicate fluoride solution carry out neutralization reaction, to filter after elimination throw out to obtain magnesium silicofluoride solution;
(3) to magnesium silicofluoride solution warms to evaporating at 105-500 DEG C, concentrated 1-6h, be decomposed into magnesium fluoride;
(4) magnesium fluoride is carried out after cooling and Tai-Ace S 150, water stirring and dissolving obtain low strength alkali-free liquid accelerator, or magnesium fluoride and trolamine, Tai-Ace S 150, water stirring and dissolving are obtained high strength alkali-free liquid accelerator.
5. preparation method according to claim 4, is characterized in that: in described step (2), the mass ratio of magnesium silicofluoride and magnesium fluoride is 1:0.28.
6. preparation method according to claim 4, is characterized in that: in described step (3), evaporation, decomposition produces SiF simultaneously
4gas and water of condensation, by SiF
4gas carries out the reaction raw materials that recovery is used as step (1), and water of condensation is returned boiler.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106517871A (en) * | 2016-11-29 | 2017-03-22 | 广西大学 | Concrete accelerator and preparation method thereof |
| CN107140867A (en) * | 2017-07-15 | 2017-09-08 | 王宇青 | Increasing material manufacturing building, structures or its component alkali-free quick-coagulant |
| CN107298540A (en) * | 2017-03-06 | 2017-10-27 | 江苏苏博特新材料股份有限公司 | A kind of anti-freezing type alkali-free quick-coagulant and preparation method and application |
| CN107337374A (en) * | 2017-07-15 | 2017-11-10 | 王宇青 | Fluorine-containing alkali-free liquid accelerator |
| CN107500592A (en) * | 2017-09-27 | 2017-12-22 | 四川铁科新型建材有限公司 | A kind of alkali-free quick-coagulant composition solution and preparation method thereof |
| CN107601944A (en) * | 2017-11-08 | 2018-01-19 | 赵前方 | A kind of alkali-free liquid accelerator |
| CN108264257A (en) * | 2018-01-08 | 2018-07-10 | 贵州天威建材科技有限责任公司 | A kind of polymer phosphate aluminium series is without chlorine without sulphur alkali-free liquid setting accelerator and preparation method thereof |
| CN110615638A (en) * | 2019-10-15 | 2019-12-27 | 天津冶建特种材料有限公司 | Low-temperature-resistant liquid alkali-free setting accelerator and preparation method thereof |
| CN111333357A (en) * | 2020-03-11 | 2020-06-26 | 四川津宏康泰新材料有限公司 | Accelerating agent and preparation method thereof |
| CN111908819A (en) * | 2020-06-18 | 2020-11-10 | 贵州石博士科技有限公司 | Liquid alkali-free accelerator and preparation method thereof |
| CN116553855A (en) * | 2023-04-12 | 2023-08-08 | 自贡市星星化学建材有限公司 | Preparation process of alkali-free accelerator |
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| CN104724971A (en) * | 2013-12-18 | 2015-06-24 | 徐州九龙合成材料厂 | Preparation method of alkali-free liquid accelerator for shotcrete |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106517871A (en) * | 2016-11-29 | 2017-03-22 | 广西大学 | Concrete accelerator and preparation method thereof |
| CN107298540A (en) * | 2017-03-06 | 2017-10-27 | 江苏苏博特新材料股份有限公司 | A kind of anti-freezing type alkali-free quick-coagulant and preparation method and application |
| CN107298540B (en) * | 2017-03-06 | 2019-07-30 | 江苏苏博特新材料股份有限公司 | A kind of anti-freezing type alkali-free quick-coagulant and the preparation method and application thereof |
| CN107337374B (en) * | 2017-07-15 | 2020-12-08 | 吉安民辉新型材料有限公司 | Fluorine-containing alkali-free liquid accelerator |
| CN107140867A (en) * | 2017-07-15 | 2017-09-08 | 王宇青 | Increasing material manufacturing building, structures or its component alkali-free quick-coagulant |
| CN107337374A (en) * | 2017-07-15 | 2017-11-10 | 王宇青 | Fluorine-containing alkali-free liquid accelerator |
| CN107500592A (en) * | 2017-09-27 | 2017-12-22 | 四川铁科新型建材有限公司 | A kind of alkali-free quick-coagulant composition solution and preparation method thereof |
| CN107601944A (en) * | 2017-11-08 | 2018-01-19 | 赵前方 | A kind of alkali-free liquid accelerator |
| CN108264257A (en) * | 2018-01-08 | 2018-07-10 | 贵州天威建材科技有限责任公司 | A kind of polymer phosphate aluminium series is without chlorine without sulphur alkali-free liquid setting accelerator and preparation method thereof |
| CN108264257B (en) * | 2018-01-08 | 2020-06-02 | 贵州天威建材科技有限责任公司 | Polymerized aluminum phosphate series chlorine-free sulfur-free liquid alkali-free setting accelerator and preparation method thereof |
| CN110615638A (en) * | 2019-10-15 | 2019-12-27 | 天津冶建特种材料有限公司 | Low-temperature-resistant liquid alkali-free setting accelerator and preparation method thereof |
| CN111333357A (en) * | 2020-03-11 | 2020-06-26 | 四川津宏康泰新材料有限公司 | Accelerating agent and preparation method thereof |
| CN111908819A (en) * | 2020-06-18 | 2020-11-10 | 贵州石博士科技有限公司 | Liquid alkali-free accelerator and preparation method thereof |
| CN116553855A (en) * | 2023-04-12 | 2023-08-08 | 自贡市星星化学建材有限公司 | Preparation process of alkali-free accelerator |
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